Heretofore, photosensitive resin compositions have been used to prepare masks for production of circuits, such as semiconductor integrated circuits (IC) and thin film transistor (TFT) circuits for liquid crystal displays (LCD), and a photosensitive resin composition capable of forming a finner pattern structure, is required.
On the other hand, a photosensitive resin composition has attracted attention also as a resist material to form ITO electrodes for LCD, an organic EL display, etc., or as a permanent film-forming material for an interlayer insulation film, a circuit-protecting film, a barrier rib material for a color filter, a barrier rib material for an organic EL display, etc. For example, in the production of a liquid crystal color filter, an ink jet method has been proposed wherein ink is applied by ink jet within fine pixels, and a photosensitive resin composition is formed into barrier ribs for the pixel pattern.
In such a case, the photosensitive resin composition to be formed into barrier ribs, is used as a permanent film-forming material and thus required to have adhesion to a substrate. Further, in order to prevent e.g. color mixing of inks between the adjacent pixel regions, it is required to have so-called ink repellency i.e. solvent repellency against the ink solvent such as water or xylene.
As such a photosensitive resin composition having ink repellency, a radiation-sensitive resin composition for forming barrier ribs for a color filter is, for example, disclosed which comprises hexafluoropropylene, an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and a fluorinated copolymer with an unsaturated compound co-polymerizable with such a component, a photoacid generator, a crosslinkable compound, a fluorinated organic compound other than the above fluorinated copolymer, and an organic solvent. As the fluorinated organic compound, an oligomer containing perfluoroalkyl group and a lipophilic group, is exemplified (Claim 1 in JP-A-11-281815).
Further, a negative resist composition for electron beam or X-ray is disclosed which comprises a compound to generate an acid and/or a radical species under irradiation with electron beam or X-ray, a resin insoluble in water and soluble in an aqueous alkaline solution, having at least one unsaturated bond polymerizable by an acid and/or radicals, a crosslinking agent to form crosslinkage with such a resin by an action of an acid, and a fluorine-type and/or silicon type surfactant (Claim 1 in JP-A-2002-6491).
Further, a photosensitive resin composition is disclosed as a low dielectric constant resin composition, which comprises an unsaturated group-containing resin having a polybasic acid anhydride reacted as the case requires with a reaction product of a copolymer made of a monomer having fluorine atoms and an ethylenic double bond and a monomer having an epoxy group and an ethylenic double bond, with a compound having one ethylenic double bond and one carboxyl group per molecule, and a saturated monocarboxylic acid as an optional component, a diluting agent, and a photopolymerization initiator. An unsaturated group-containing resin is exemplified wherein a copolymer made of trifluoroethyl methacrylate and glycidyl methacrylate, is reacted with acrylic acid, and then reacted with succinic anhydride (Claims 1 and 2 in JP-A-2001-253928).
Further, a covering agent is disclosed which comprises a hydrocarbon monomer containing at least one group selected from an acryloyl group, a methacryloyl group and a vinyl group per molecule, and a copolymer having acryloyl groups or methacryloyl groups, of a structure wherein an isocyanate group of an isocyanate group- and an acryloyl or methacryloyl group-containing monomer is addition-reacted to hydroxyl groups of a polymer obtained by reacting a C3-20 perfluoroalkyl group-containing α,β-unsaturated monomer, a polysiloxane chain-containing α,β-unsaturated monomer, a no perfluoroalkyl group-containing and no polysiloxane chain-containing hydroxyl group-containing α,β-unsaturated monomer, as essential components (Claim 1 of JP-A-8-176504).
However, in the resin compositions disclosed in the above JP-A-11-281815 and JP-A-2002-6491, no ethylenic double bond is contained in the exemplified ink repellent component such as the fluorinated organic compound or the fluorine and/or silicone type surfactant. Accordingly, when such a fluorinated compound was applied to a radical-curable composition, curing of the ink repellent component tended to be inadequate, whereby the durability of the ink repellency tended to be inadequate.
Whereas, the unsaturated group-containing resin disclosed in JP-A-2001-253928 is intended to lower the dielectric constant, and with the exemplified compound, the ink repellency was inadequate. Further, in the photosensitive resin composition disclosed in JP-A-2001-253928, an alkali-soluble resin containing fluorine atoms was used, whereby the adhesion to the substrate was inadequate. Further, with such a photosensitive resin composition, the developability was inadequate, and it was difficult to form fine patterns.
Further, the hydrocarbon monomer in the covering agent disclosed in JP-A-8-176504 had a difficulty in providing a difference in the alkali solubility between an exposed portion and a non-exposed portion, whereby it was difficult to form fine patterns.
Accordingly, it is an object of the present invention to provide a negative photosensitive resin composition which is excellent in the adhesion to a substrate, the ink repellency and the durability thereof and which is further excellent in the developability.